Panayot Petrov, John Entwisle, Heidi Goenaga-Infante GC-ICP-MS reference methodology to quantify polybrominatedflame retardants in environmental waters relevant to the European Water Frame Directive.

European Metrology Research

• Traceable measurements for monitoring critical pollutants under the European Water Framework Directive– Duration 10/2011 to 09/2014

– Participants: BAM, BRML, IJS, JRC, LGC, LNE, PTB, SYKE, TUBITAK UME , UBA, ISPRA, REG(HZG)

– Target analytes: TBT, PAH, PBDE

• LGC involvement in ENV08 WFD– WP2 – Development of a validated measurement procedure for PBDE

in whole water samples at a concentration level required by the WFD

– WP4 – Advanced analytical platforms for monitoring the interaction and partitioning of pollutants in environmental aquatic compartments

Metrological aims

• Reference method for determination of PBDE in whole (non-filtered) water– Congeners of interest – PBDE 28, 47, 99, 100, 153, 154– Required LOQs – Σ(6 PBDEs) ≤ 0.15 ng/L in whole water

– Measurement uncertainty (95 % confidence) ≤ 50 % at EQS

• Systematic study of the interaction and partitioning of pollutants by field flow fractionation techniques– Distribution of the pollutants among fractions of different size and type;

– Elucidation of interactions / partitioning– Mass balance data for the size based distribution

Development of a validated measurement procedure for PBDE in whole water samples at a concentration level

required by the WFD

Advanced analytical platforms for monitoring the interaction and partitioning of pollutants in environmental

aquatic compartments

Chromatographic separation of the target PBDEs

• Short program– Species separated in 3.5 min

– Sample throughput – 4 samples per hour– Baseline separation of the target congeners

– Suitable for pre-screening for “above/below EQS”

• Long program– Species separated in 28 min– Sample throughput – 0.5 samples per hour (2h/sample)

– Separation of up to 180 PBDE congeners*

– Suitable for more accurate congener identification in case of PBDE concentrations > EQS level

*J. Chrom. A, 1217, 17, (2010), 2964–2972

Chromatographic separation of the target PBDEs

153154

99

100

47

28

0

20

40

60

80

100

120

140

160

180

200

0 50 100 150 200 250 300 350 400 450 500 550 600 650 700

Time [sec]

Br S

igna

l [K

cps]

Br79 Br81

153

15499

10047

28

0

5

10

15

20

25

30

35

40

45

50

0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 7000

Time [sec]

Br S

igna

l [K

cps]

Br79 Br81

Long GC separation method

Short GC separation method

Chromatographic separation / detection of the target PBDEs by HPLC-ICP-MS

0

50

100

150

200

250

0 1000 2000 3000 4000 5000 6000 7000

Time [sec]

Br S

igna

l [K

cps]

0

1

2

3

4

5

6

7

124X

e si

gnal

[Mcp

s]

Br79 Br81 124

PBDE 28PBDE 47

PBDE 100 PBDE 99

PBDE 154

PBDE 153

NIST 22571+19 diluted in n-hexane

0

200

400

600

800

1000

1200

1400

1600

0 100 200 300 400 500 600 700 800 900 1000

Time [sec]

Br S

igna

l [K

cps]

Br79 Br81

PBDE 28

PBDE 47

0

100

200

300

400

500

600

700

800

510 530 550 570 590 610

Time [sec]

Br

Sign

al [K

cps]

Br79 Br81

PBDE 100PBDE 99

PBDE 154PBDE 153

NIST 22571+19 diluted in n-hexane

Chromatographic separation / detection of the target PBDEs by HPLC-ICP-MS

Limits of detection for target PBDEs

• Limits of detection with external calibration– Instrumental detection limits – below 1ng/ml Br; calculated as 3 X noise

band width, expressed concentration based on external calibration by peak height

– Similar for both Br isotopes (79Br, 81Br)

– Similar for both Q-ICP-MS and SF-ICP-MS detectors– PBDE based IDLs ~ 1ng/ml

– Current method detection limits – 25 fg/mL as Br

– Current preconcentration factor – 40 000 X

Detection limits of the target PBDEs

• Instrument detection limits – Q-ICP-MS

0

2

4

6

8

10

12

14

16

6.5 7 7.5 8 8.5 9 9.5 10 10.5 11

Time [min]

79B

r Sig

nal [

Kcp

s]

-12

-7

-2

3

8

13

18

81B

r Sig

nal [

Kcp

s]

79Br 81Br

1531549910047

1.56 ng/ml Br

28

Detection limits of the target PBDEs

• Instrument detection limits – SF-ICP-MS

1 .5

2 .5

3 .5

4 .5

5 .5

6 .5

7 .5

8 .5

9 .5

40 0 4 50 50 0 5 50 60 0 6 50

Tim e [s]

Sig

na

l [k

cps]

7 9Br 8 1Br

28

47 100

99154

153

1 ng/ml Br

Preconcentration ProcedureRecoveries

0

20

40

60

80

100

120

PBDE 28 PBDE 47 PBDE 99 PBDE 100 PBDE 153 PBDE 154

Rec

over

y %

at 3

ng/

L

79Br 81Br

•Vary with the congener

•Consistent with relatively large uncertainty

•3 samples, each spiked with ~ 3 ng/L of each congener:

0

100

200

300

400

500

600

700

0 100 200 300 400 500 600 700 800 900

Time [s]

79B

r Sig

nal [

kcps

]

ENV08 spiked ENV08

?

Finnish River Water Analysis

0

50

100

150

200

250

300

0 100 200 300 400 500 600 700 800 900Time [s]

79B

r Sig

nal [

kcps

]

Procedural blank Standards blend

28

47

100

99

154153

?

C= 1.25 ng/LR= 72 to 100%

Thames River Water Analysis

0

20

40

60

80

100

120

4 5 6 7 8 9 10 11

Time [min]

79B

r S

igna

l [K

cps]

PBDE 470.05 ng/L

PBDE 990.2 ng/L

Development of a validated measurement procedure for PBDE in whole water samples at a concentration level

required by the WFD

Advanced analytical platforms for monitoring the interaction and partitioning of pollutants in environmental

aquatic compartments

Fractionation of environmental water samples and NOMs

•Method development samples – Finnish river water, Thames

River water, Suwannee River NOM and Nordic Reservoir

NOM(IHSS), HA and HA-Na (Sigma)

•Size/mass calibrants – 1, 300, 1000 kDa PSS; Spherical S-PS

100, 200 nm; NIST gold nano-particles 10, 30, 60 nm spheres

•Detection:

- Online –> UV-MALS-ICPMS for size and elemental

composition

- Offline –> GC-SF-ICPMS for PBDEs association /

distribution on nano-particles

Fractionation of Finnish Water Sample

0

20

40

60

80

100

120

140

0 10 20 30 40 50 60 70 80Time [min]

Sig

nal [

kcps

]

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

Br s

igna

l [kc

ps]

Al27 Mn55 Fe57 Cu63 Cu65 Zn66 Sn118 Sn119 Sn120 Br79 Br81

0

1

2

3

4

5

6

7

8

9

10

0 10 20 30 40 50 60 70 80Time [min]

Sig

nal [

kcps

]

Al27 Mn55 Fe57 Cu63 Cu65 Zn66 Sn118 Sn119 Sn120

Fractionation of Thames River Water Samples

0

50

100

150

200

250

0 500 1000 1500 2000 2500 3000 3500 4000

time [s]

Sig

nal [

kcps

]

-2.5

-1.5

-0.5

0.5

1.5

2.5

3.5

4.5

Br s

igna

l [kc

ps]

Al27 Mn55 Fe57 Cu63 Cu65 Zn66 Sn118 Sn119 Sn120 Br79 Br81

0

2

4

6

8

10

12

14

16

18

20

0 500 1000 1500 2000 2500 3000 3500 4000

time [s]

Sig

nal [

kcps

]

Al27 Mn55 Fe57 Cu63 Cu65 Zn66 Sn118 Sn119 Sn120

100 ppm 1, 300, 1000 kDa PSS in 0.9% NaCl, 5 mM NH 4NO3 carrier

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0 10 20 30 40 50 60 70 80 90 100

Time [min]

UV

Sig

nal a

t 236

nm [V

]

-0.80

-0.75

-0.70

-0.65

-0.60

-0.55

-0.50

-0.45

-0.40

UV

Sig

nal a

t 254

nm [V

]

1 kDa

300 kDa

1000 kDa

Calibrant Fractograms

Nist Au 10, 30, 60 nm spheres

0

20

40

60

80

100

120

140

0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 7000

Time [s]

Sig

nal [

kcps

]

Field

release

100, 200nm S-PS in 5 mM NH 4NO3 carrier

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0 10 20 30 40 50 60 70 80 90 100Time [min]

UV

Sig

nal a

t 236

nm [

V]

-0.80

-0.60

-0.40

-0.20

0.00

0.20

0.40

0.60

0.80

UV

Sig

nal a

t 254

nm [

V]

236 nm 254 nm

100 nm

200 nm

Field

release

Size Calibrants Fractogramsand MALS Size Estimation

Radius

Time [min]6560555045

Rad

ius

[nm

]

85

80

75

70

65

60

55

50

45

40

35

Detector S

ignal[V]

0.0

- MALS calculated diameters 92 nm and 212 nm

100, 200nm S-PS in 5 mM NH 4NO3 carrier

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0 10 20 30 40 50 60 70 80 90 100Time [min]

UV

Sig

nal a

t 236

nm [

V]

-0.80

-0.60

-0.40

-0.20

0.00

0.20

0.40

0.60

0.80

UV

Sig

nal a

t 254

nm [

V]

236 nm 254 nm

100 nm

200 nm

Field

release

Fractograms of HA -Na and PBDE spiked HA -Na

1 0 0 p p m H A - N a i n 5 m M N H 4 N O 3

0 . 0

0 . 2

0 . 4

0 . 6

0 . 8

1 . 0

1 . 2

1 . 4

1 . 6

1 . 8

2 . 0

0 5 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5 7 0 7 5 8 0

T i m e [ m i n ]

Sig

nal [

kcp

s]B r 7 9 B r 8 1

1 0 0 p p m H A - N a + 2 5 0 p p b P B D E

0 . 0

0 . 5

1 . 0

1 . 5

2 . 0

2 . 5

3 . 0

3 . 5

4 . 0

4 . 5

5 . 0

0 5 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5 7 0 7 5 8 0

T i m e [ m i n ]

Sig

nal [

kcps

]

B r 7 9 B r 8 1

ASF4 offline GC -SF-ICP-MS analysis of HA -Na

• 2 x 1 ml HA-Na 100ppm, 30 ml fraction, 50µl extract volume

8

18

28

38

48

58

68

6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0Time [min]

79B

r sig

nal i

n H

A-N

A s

ampl

e [k

cps]

-10

-5

0

5

10

15

20

79B

r sig

nal i

n a

stan

dard

[kcp

s]

HA-Na PBDEs standard

PBDE-47

PBDE-100

PBDE-99

U1

U2

PBDE-28

PBDE-154

PBDE-153

PBDE-99

PBDE-47

ASF4 offline GC -SF-ICP-MS analysis of HA -Na

• 2 x 1 ml HA-Na 100 mg/L + 500 ng/ml PentaBDE (DE-71)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0

Time [min]

79B

r in

HA

-Na

spi

ked

sam

ple

[Mcp

s]

-10

-5

0

5

10

15

20

79B

r si

gna

l in

a st

anda

rd [k

cps]

PBDE spiked HA-Na sample PBDEs standard

PBDE-47

PBDE-100

PBDE-99PBDE-28

PBDE-154PBDE-153

PBDE-100

PBDE-154 PBDE-153U2U1PBDE-28

Future prospective

• Improve the limits of detection to reach the WFD requirements• Employ 81Br isotopically enriched PBDE species for

quantification of PBDEs in natural water samples • Use FFF in combination with conventional fractionation

techniques to better characterize the interaction and partitioning of PBDEs in water samples, rich in organic and inorganic colloids.

• Validate the methodology and prepare uncertainty budget for quantification of PBDEs in natural waters after LLE, species specific double ID-ICP-MS quantification

Thank you for your attention …

The authors are grateful to EMRP and NMO for sponsoring this research, to Volker Nischwitz, who helped with the method development for WP2 and WP4,to Christopher Hopley for his highly valued advice in GC method development and troubleshooting, and last but not least to all our partners and colleagues, without whom this research wouldn’t be possible.

Acknowledgements: